MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present application concerns compounds for use in electronic devices, processes for preparing the compounds, and electronic devices comprising the compounds.

Claims

1.-20. (canceled)

21. A compound of formula (I) ##STR00483## where the following applies to the variable groups: Z is C, if a group —[Ar.sup.2].sub.n-A is bonded to it; and Z is selected, identically or differently at each occurrence, from CR.sup.1 and N, if no group —[Ar.sup.2].sub.n-A is bonded to it; Y is C, if a group Ar.sup.1 is bonded to it; and Y is selected, identically or differently on each occurrence, from CR.sup.3 and N, if no group Ar.sup.1 is bonded to it; X is O or S; Ar.sup.1 is, identically or differently at each occurrence, selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted by radicals R.sup.4, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which are substituted by radicals R.sup.4; Ar.sup.2 is, identically or differently at each occurrence, selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted by radicals R.sup.5, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which are substituted by radicals R.sup.5; A corresponds to the following formula ##STR00484##  which is bonded via the dotted line; Ar.sup.3 and Ar.sup.4 are, identically or differently at each occurrence, selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted by radicals R.sup.5, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, which are substituted by radicals R.sup.5; T is a single bond or a divalent group selected from C(R.sup.5).sub.2, Si(R.sup.5).sub.2, N(R.sup.5), O, and S; k is 0 or 1, where k=0 means that T does not occur and the groups Ar.sup.3 and Ar.sup.4 are not connected; R.sup.1 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.1 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems are in each case substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.2 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems are in each case substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.3 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.3 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems are in each case substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.4 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.4 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems are in each case substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.5 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.5 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems are in each case substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.6 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, C(═O)R.sup.7, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, P(═O)(R.sup.7).sub.2, OR.sup.7, S(═O)R.sup.7, S(═O).sub.2R.sup.7, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.6 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems are in each case be substituted by radicals R.sup.7, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by —R.sup.7C═CR.sup.7—, —C≡C—, Si(R.sup.7).sub.2, C═O, C═NR.sup.7, —C(═O)O—, —C(═O)NR.sup.7—, NR.sup.7, P(═O)(R.sup.7), —O—, —S—, SO or SO.sub.2; R.sup.7 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN; m is 1, 2, 3, or 4; n is 0, 1, 2, 3, or 4.

22. The compound according to claim 21, wherein it is a monoamine.

23. The compound according to claim 21, wherein the group —[Ar.sup.2].sub.n-A is bonded in position 2 or 4, on the fluorene sub-structure of formula (I).

24. The compound according to claim 21, wherein X is O.

25. The compound according to claim 21, wherein m is 1 or 2.

26. The compound according to claim 21, wherein groups —[Ar.sup.1].sub.m— for the case of m=1 are selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene, where the phenylene groups are substituted with radicals R.sup.4.

27. The compound according to claim 21, wherein n is 0, so that the group Ar.sup.2 is not present, and the fluorene moiety and the amine nitrogen in formula (I) are directly connected to each other.

28. The compound according to claim 21, wherein n is 1.

29. The compound according to claim 28, wherein group —[Ar.sup.2].sub.n— is selected from divalent groups derived from phenyl, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, which are substituted with radicals R.sup.5.

30. The compound according to claim 21, wherein k=0, i.e. groups Ar.sup.3 and Ar.sup.4 in group A are not linked to each other by a group T.

31. The compound according to claim 21, wherein Ar.sup.3 and Ar.sup.4 are selected, identically or differently, from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-condensed dibenzofuranyl, benzo-condensed dibenzothiophenyl, phenyl substituted with naphthyl, phenyl substituted with fluorenyl, phenyl substituted with spirobifluorenyl, phenyl substituted with dibenzofuranyl, phenyl substituted with dibenzothiophene, phenyl substituted with carbazolyl, phenyl substituted with pyridyl, phenyl substituted with pyrimidyl, and phenyl substituted with triazinyl, where the groups are each substituted with radicals R.sup.5.

32. The compound according to claim 21, wherein R.sup.1 is selected, identically or differently, from H, D, F, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl and alkoxy groups and the said aromatic and heteroaromatic ring systems are substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl and alkoxy groups may in each case be replaced by —C≡C—, —R.sup.6C═CR.sup.6—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —NR.sup.6—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.6—; and R.sup.2 is F, Si(R.sup.6).sub.3, a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, or a heteroaromatic ring system having 5 to 40 aromatic ring atoms; where the said alkyl group and the said aromatic or heteroaromatic ring system are substituted by radicals R.sup.6; and R.sup.3 is selected, identically or differently, from H, D, F, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl and alkoxy groups and the said aromatic and heteroaromatic ring systems are substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl and alkoxy groups may in each case be replaced by —C≡C—, —R.sup.6C═CR.sup.6—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —NR.sup.6—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.6—; and R.sup.4 is selected, identically or differently, from H, D, F, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl and alkoxy groups and the said aromatic and heteroaromatic ring systems are substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl and alkoxy groups may in each case be replaced by —C≡C—, —R.sup.6C═CR.sup.6—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —NR.sup.6—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.6—; and R.sup.5 is selected, identically or differently, from H, D, F, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl and alkoxy groups and the said aromatic and heteroaromatic ring systems are substituted by radicals R.sup.6, and where one or more CH.sub.2 groups in the said alkyl and alkoxy groups may in each case be replaced by —C≡C—, —R.sup.6C═CR.sup.6—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —NR.sup.6—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.6—; and R.sup.6 is selected, identically or differently, from H, D, F, CN, Si(R.sup.7).sub.3, N(R.sup.7).sub.2, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl and alkoxy groups and the said aromatic and heteroaromatic ring systems are substituted by radicals R.sup.7, and where one or more CH.sub.2 groups in the said alkyl and alkoxy groups may in each case be replaced by —C≡C—, —R.sup.7C═CR.sup.7—, Si(R.sup.7).sub.2, C═O, C═NR.sup.7, —NR.sup.7—, —O—, —S—, —C(═O)O— or —C(═O)NR.sup.7—.

33. The compound according to claim 21, wherein R.sup.2 is selected from the following groups ##STR00485## where the dotted bond represents the bond to the rest of the formula.

34. The compound according to claim 21, wherein the compound conforms to one of the following formulae ##STR00486## ##STR00487## where X is selected, identically or differently, from O and S.

35. A method for preparation of the compound of formula (I) according to claim 21, wherein a biphenyl derivative which is substituted with two reactive groups, of which at least one is present in the ortho-position to the phenyl-phenyl bond of the biphenyl derivative, is metalated.

36. An oligomer, polymer or dendrimer, comprising one or more compounds of formula (I) according to claim 21, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions in formula (I) substituted by R.sup.1, R.sup.2, R.sup.3, R.sup.4, or R.sup.5.

37. A formulation, comprising at least one compound of formula (I) according to claim 21 and at least one solvent.

38. An electronic device, comprising at least one compound according to claim 21.

39. The electronic device according to claim 38, wherein the device is an organic electroluminescent device, comprising anode, cathode and at least one emitting layer, where at least one organic layer of the device, which is a hole transport layer, an electron blocking layer or a hole injection layer, comprises the at least one compound.

40. A method comprising incorporating the compound according to claim 21 in an electronic device.

Description

EXAMPLES

A) Synthesis Examples

[0160] The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials are commercially available. The numbers in square brackets in the case of the starting materials known from the literature are the corresponding CAS numbers.

Synthesis of 6-[4-(2-chloro-9-phenyl-9H-fluoren-9-yl)phenyl]-8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaene 2a

[0161] ##STR00184##

Synthesis of 6-(4-benzoylphenyl)-8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaene 1a

[0162] ##STR00185##

[0163] 50 g (191.5 mmol) of (4-bromo-phenyl)-phenyl-methanone and 50.7 g (239.4 mmol) of dibenzofuran-4-yl-boronic acid, 26.5 g (23 mmol, 0.12 eq.) of Pd(P(Ph.sub.3)).sub.4, and 680 mL 2M solution (1365 mmol, 7 eq.) of Na.sub.2CO.sub.3 are dissolved in 1300 mL of ethylenglycoldiethylether. The reaction mixture is stirred under reflux and agitated under an argon atmosphere for 12 hours. After cooling to room temperature, the mixture is extracted with ethyl acetate. The organic phase is dried with Na.sub.2SO.sub.4 and the filtrate is evaporated in vacuo, and the residue is purified by chromatography (mixture heptane/AcOEt). The product is isolated in the form of an off-white solid (46 g, 68% of theory).

[0164] The synthesis of further derivatives is carried out analogously:

TABLE-US-00001 Ex. Boronic acid Bromide Product Yield 1b [00186] [00187] [00188] 76% 1c [00189] [00190] [00191] 74% 1d [00192] [00193] [00194] 80% 1f [00195] [00196] [00197] 70% 1g [00198] [00199] [00200] 86% 1h [00201] [00202] [00203] 71% 1i [00204] [00205] [00206] 77% 1j [00207] [00208] [00209] 65% 1k [00210] [00211] [00212] 81% 1l [00213] [00214] [00215] 70% 1ll [00216] [00217] [00218] 71% 1m [00219] [00220] [00221] 76% 1n [00222] [00223] [00224] 81% 1o [00225] [00226] [00227] 68% [00228] 1p [00229] [00230] [00231] 80%

Synthesis of Synthesis of 6-[4-(2-chloro-9-phenyl-9H-fluoren-9-yl)phenyl]-8-oxatricyclo[7.4.0.0.SUP.2,7.]trideca-1(13),2,4,6,9,11-hexaene 2a

[0165] ##STR00232##

[0166] A solution of 2-bromo-4′-chloro-biphenyl (43 g, 158 mmol) in THF (465 ml) is treated with 58 mL of n-BuLi (2.2 M in hexane, 144 mmol) under argon at −78° C. The mixture is stirred for 30 minutes. A solution of 1a (50 g, 144 mmol) in 230 mL THF is added dropwise. The reaction proceeds at −78° C. for 30 minutes and then is stirred at room temperature overnight. The reaction is quenched with water and the solid is filtered. Without further purification, a solution of the alcohol in 700 mL toluene and 2.9 g p-toluenesulfonic acid is refluxed overnight. After cooling, the organic phase is washed with water and the solvent is removed under vacuum. The product is isolated in the form of a white solid (55 g, 74% of theory).

[0167] The following compounds are synthesized analogously:

TABLE-US-00002 Ex. Ketone Halogen Product Yield 2b [00233] [00234] [00235] 81% 2c [00236] [00237] [00238] 72% 2d [00239] [00240] [00241] 33% 2e [00242] [00243] [00244] 82% 2f [00245] [00246] [00247] 80% 2g [00248] [00249] [00250] 75% 2h [00251] [00252] [00253] 75% 2i [00254] [00255] [00256] 64% 2j [00257] [00258] [00259] 60% 2k [00260] [00261] [00262] 70% 2l [00263] [00264] [00265] 80% 2m [00266] [00267] [00268] 75% 2n [00269] [00270] [00271] 80% 2o [00272] [00273] [00274] 77% 2p [00275] [00276] [00277] 82% 2q [00278] [00279] [00280] 84% 2r [00281] [00282] [00283] 78% 2s [00284] [00285] [00286] 74% 2t [00287] [00288] [00289] 70%

Synthesis of N-{[1,1′-biphenyl]-4-yl}-N-(9,9-dimethyl-9H-fluoren-2-yl)-9-(4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]tridecal (9),2,4,6,10,12-hexaen-6-yl}phenyl)-9-phenyl-9H-fluoren-2-amine 4a

[0168] ##STR00290##

[0169] S-Phos (0.645 g, 1.6 mmol), Pd.sub.2(dba).sub.3 (0.72 g, 0.8 mmol) and sodium tert-butoxide (5 g, 52.4 mmol) are added to a solution of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-amine (9.5 g, 26.2 mmol) and fluorene 3a (9.5 g, 26.2 mmol) in degassed toluene (140 ml), and the mixture is heated under reflux for 10 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from toluene/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice. The product is isolated in the form of an off-white solid (11 g, 40% of theory).

[0170] The following compounds are obtained analogously:

TABLE-US-00003 Halogenated Ex. Fluorene Amine Product Yield 4b [00291] [00292] [00293] 53% 4c [00294] [00295] [00296] 65% 4d [00297] [00298] [00299] 51% 4e [00300] [00301] [00302] 62% 4f [00303] [00304] [00305] 58% 4g [00306] [00307] [00308] 63% 4h [00309] [00310] [00311] 55% 4i [00312] [00313] [00314] 77% 4j [00315] [00316] [00317] 76% 4k [00318] [00319] [00320] 65% 4l [00321] [00322] [00323] 52% 4m [00324] [00325] [00326] 73% 4n [00327] [00328] [00329] 59% 4o [00330] [00331] [00332] 55% 4p [00333] [00334] [00335] 55% 4q [00336] [00337] [00338] 75% 4r [00339] [00340] [00341] 70% 4s [00342] [00343] [00344] 72% 4t [00345] [00346] [00347] 62% 4u [00348] [00349] [00350] 45% 4v [00351] [00352] [00353] 66% 4w [00354] [00355] [00356] 66% 4x [00357] [00358] [00359] 71% 4y [00360] [00361] [00362] 49% 4z [00363] [00364] [00365] 65% 4aa [00366] [00367] [00368] 73% 4ab [00369] [00370] [00371] 70% 4ac [00372] [00373] [00374] 80% 4ad [00375] [00376] [00377] 75% 4ae [00378] [00379] [00380] 50% 4af [00381] [00382] [00383] 40% 4ag [00384] [00385] [00386] 76% 4ah [00387] [00388] [00389] 54% 4ai [00390] [00391] [00392] 47% 4aj [00393] [00394] [00395] 40% 4ak [00396] [00397] [00398] 37% 4al [00399] [00400] [00401] 42% 4am [00402] [00403] [00404] 51% 4an [00405] [00406] [00407] 47%

Synthesis of N-{[1,1′-biphenyl]-4-yl}-9,9-di methyl-N-{4-[9-(4-{8-oxatricyclo[7.4.0.0.SUP.2,7.]tridecal (13),2(7),3,5,9,11-hexaen-6-yl}phenyl)-9-phenyl-9H-fluoren-2-yl]phenyl}-9H-fluoren-2-amine 5a

[0171] ##STR00408##

[0172] 59.1 g (101.8 mmol) of Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine, 52.8 g (101.8 mmol) fluorene 3a, 3.88 g (5.14 mmol) of PdCl.sub.2(Cy).sub.3, 31.2 g (205.6 mmol) of cesium fluoride are dissolved in 800 mL of toluene. The reaction mixture is refluxed and agitated under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice. The product is isolated in the form of a white solid (46 g, 50% of theory).

[0173] The following compounds are synthesized analogously:

TABLE-US-00004 Halogenated Ex. fluorene Amine Product Yield 5b [00409] [00410] [00411] 53% 5c [00412] [00413] [00414] 65% 5d [00415] [00416] [00417] 50% 5e [00418] [00419] [00420] 53% 5f [00421] [00422] [00423] 60% 5g [00424] [00425] [00426] 55% 5h [00427] [00428] [00429] 65% 5i [00430] [00431] [00432] 54% 5j [00433] [00434] [00435] 65% 5k [00436] [00437] [00438] 45% 5l [00439] [00440] [00441] 80% 5m [00442] [00443] [00444] 67% 5n [00445] [00446] [00447] 60% 5o [00448] [00449] [00450] 50% 5p [00451] [00452] [00453] 62% 5q [00454] [00455] [00456] 55% 5r [00457] [00458] [00459] 66% 5s [00460] [00461] [00462] 52% 5t [00463] [00464] [00465] 47% 5u [00466] [00467] [00468] 53%

B) Device Examples

B-1) General Preparation and Characterization Methods

[0174] OLEDs comprising compounds according to the present application are prepared by the following general process: The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have the following layer structure: substrate/hole-injection layer (HIL)/hole-transport layer (HTL)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The specific device setup of the OLEDs is shown in Tables 1a to 1c, and the materials for the various layers of the OLEDs are shown in Table 3.

[0175] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by coevaporation. An expression such as H:SEB (5%) here means that material H is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion by volume of 5%. Analogously, other layers may also consist of a mixture of two or more materials.

[0176] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80 @ 60 mA/cm.sup.2 is the lifetime until at a current density of 60 mA/cm.sup.2, the OLED has dropped from its initial luminance of e.g. 5000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4000 cd/m.sup.2 without using any acceleration factor.

B-2) Use of the Compounds in the EBL of Blue Fluorescent OLEDs

[0177] The compounds HTM-1 to HTM-3 according to the present application are used in the EBL of a blue fluorescent OLED stack, as shown below in Table 1a.

TABLE-US-00005 TABLE 1a Device Setup HTL EBL ETL EIL HIL Thickness/ Thickness/ EML Thickness/ Thickness/ Ex. Thickness/nm nm nm Thickness/nm nm nm E1 HTM: p-dopant (5%) HTM HTM-1 H: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E2 HTM: p-dopant (5%) HTM HTM-2 H: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E3 HTM: p-dopant (5%) HTM HTM-3 H: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

[0178] In such device setup, very good results for EQE, lifetime and voltage are obtained with the compounds, as shown in the table below.

TABLE-US-00006 TABLE 2a Data for the OLEDs U @ 10 EQE @ 10 LT80 @ 60 Ex. mA/cm.sup.2 (V) mA/cm.sup.2 (%) mA/cm.sup.2 ( h) E1 4.1 9.1 230 E2 3.8 8.2 230 E3 3.9 8.5 270

B-3) Use of the Compounds in the EBL of Green Phosphorescent OLEDs

[0179] The compounds HTM-1 to HTM-4 according to the present application are used in the EBL of a blue fluorescent OLED stack, as shown below in Table 1b.

TABLE-US-00007 TABLE 1b Device Setup HTL EBL ETL EIL HIL Thickness/ Thickness/ EML Thickness/ Thickness/ Ex. Thickness/nm nm nm Thickness/nm nm nm E4 HTM: p-dopant (5%) HTM HTM-1 TMM-1: TMM-2 ETM: LiQ(50%) LiQ 20 nm 220 nm 10 nm (28%):TEG(12%) 30 nm 1 nm 30 nm E5 HTM: p-dopant (5%) HTM HTM-2 TMM-1: TMM-2 ETM: LiQ(50%) LiQ 20 nm 220 nm 10 nm (28%):TEG(12%) 30 nm 1 nm 30 nm E6 HTM: p-dopant (5%) HTM HTM-3 TMM-1: TMM-2 ETM: LiQ(50%) LiQ 20 nm 220 nm 10 nm (28%):TEG(12%) 30 nm 1 nm 30 nm E7 HTM: p-dopant (5%) HTM HTM-4 TMM-1: TMM-2 ETM: LiQ(50%) LiQ 20 nm 220 nm 10 nm (28%):TEG(12%) 30 nm 1 nm 30 nm

[0180] In such device setup, very good results for EQE, lifetime and voltage are obtained with the compounds, as shown in the table below.

TABLE-US-00008 TABLE 2b Data for the OLEDs U @ 10 EQE @ 10 LT80 @40 Ex. mA/cm.sup.2 (V) mA/cm.sup.2 (%) mA/cm.sup.2 (h) E4 4.2 18.0 300 E5 3.8 16.1 350 E6 3.9 16.8 320 E7 4.3 16.7 280

B-4) Use of the Compounds in the HTL of Blue Fluorescent OLEDs

[0181] The compounds HTM-2 and HTM-3 according to the present application are used in the HTL of a blue fluorescent OLED stack, as shown below in Table 1c.

TABLE-US-00009 TABLE 1c Device Setup HTL EBL ETL EIL HIL Thickness/ Thickness/ EML Thickness/ Thickness/ Ex. Thickness/nm nm nm Thickness/nm nm nm E8 HTM-2: p-dopant (5%) HTM-2 EBM H: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm E9 HTM-3: p-dopant (5%) HTM-3 EBM H: SEB(5%) ETM: LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 30 nm 1 nm

[0182] In such device setup, very good results for EQE, lifetime and voltage are obtained with the compounds, as shown in the table below.

TABLE-US-00010 TABLE 2c Data for the OLEDs U @ 10 EQE @ 10 LT80 @ 60 Ex. mA/cm.sup.2 (V) mA/cm.sup.2 (%) mA/cm.sup.2 (h) E8 4.3 8.9 220 E9 4.2 8.2 300

TABLE-US-00011 TABLE 3 Materials for the OLEDs [00469] p-dopant [00470] HTM [00471] EBM [00472] H [00473] SEB [00474] TMM-1 [00475] TMM-2 [00476] TEG [00477] ETM [00478] LiQ [00479] HTM-1 [00480] HTM-2 [00481] HTM-3 [00482] HTM-4